Liquid crystal compounds having a chiral fluorinated terminal portion

ABSTRACT

Fluorine-containing, chiral liquid crystal compounds comprise (a) a chiral fluorochemical terminal portion containing at least one methylene group and optionally containing at least one catenary ether oxygen atom; (b) a saturated, chiral or achiral, hydrocarbon terminal portion; and (c) a central core connecting the terminal portions. The compounds have smectic mesophases or latent smectic mesophases and are useful, for example, in liquid crystal display devices.

FIELD OF THE INVENTION

This invention relates to fluorinated chiral smectic liquid crystalcompounds, to a process for the preparation of such compounds (and tointermediates for use therein), and to liquid crystal compound mixturesand electrooptical display devices containing such compounds.

BACKGROUND OF THE INVENTION

Devices employing liquid crystals have found use in a variety ofelectrooptical applications, in particular those which require compact,energy-efficient, voltage-controlled light valves, e.g., watch andcalculator displays, as well as the flat-panel displays found inportable computers and compact televisions. Liquid crystal displays havea number of unique characteristics, including low voltage and low powerof operation, which make them the most promising of the non-emissiveelectrooptical display candidates currently available.

One of the most important characteristics of a liquid crystal displaydevice is its response time, i.e., the time required for the device toswitch from the on (light) state to the off (dark) state. In aferroelectric or anti-ferroelectric device, response time (τ=η/P_(s) E)is proportional to the rotational viscosity (η) of the liquid crystalcompound(s) contained within the device and is inversely proportional totheir polarization (P_(s)) and to the applied electric field (E). Thus,response time can be reduced by using compound(s) having highpolarizations or low viscosities, and such compounds are greatly desiredin the art. In addition to fast response times, compounds should ideallypossess broad smectic temperature ranges to enable operation of thedevice over a broad range of temperatures (or should be capable ofcombination with other liquid crystal compounds having different smectictemperature ranges without adversely affecting the smectic phasebehavior of the base mixture).

SUMMARY OF THE INVENTION

Briefly, in one aspect, this invention provides fluorine-containing,chiral liquid crystal compounds having smectic mesophases or latentsmectic mesophases. (Compounds having latent smectic mesophases arethose which by themselves do not exhibit a smectic mesophase, but which,when in admixture with compounds having smectic mesophases or with othercompounds having latent smectic mesophases, develop smectic mesophasesunder appropriate conditions.) The chiral liquid crystal compounds ofthe invention comprise (a) a chiral fluorochemical terminal portioncontaining at least one methylene group and optionally containing atleast one catenary, i.e., in-chain, ether oxygen atom; (b) a saturated,chiral or achiral, hydrocarbon terminal portion; and (c) a central coreconnecting the terminal portions. The chiral fluorochemical terminalportion can be represented by the formula --D--R*--D--(O)_(x) --CH₂--D'--R_(f), where R* is a cyclic or acyclic chiral moiety; x is aninteger of 0 or 1; R_(f) is fluoroalkyl, perfluoroalkyl, fluoroether, orperfluoroether; and D' and each D are independently andnon-directionally selected from the group consisting of a covalent bond,##STR1## and combinations thereof, where r and r' are independentlyintegers of 0 to about 20, s is independently an integer of 1 to about10 for each (C_(s) H_(2s) O), t is an integer of 1 to about 6, and p isan integer of 0 to about 4. When the R_(f) group of the fluorochemicalterminal portion is perfluoroalkyl or perfluoroether, it can containsmall amounts of residual carbon-bonded hydrogen atoms but is preferablycompletely fluorinated. Preferably, R_(f) is fluoroalkyl, fluoroether,or perfluoroether; more preferably, R_(f) is perfluoroether, as theperfluoroether-containing compounds of the invention exhibit, e.g., abroad smectic C mesophase, good compatibility with other smectic Ccompounds, and advantageous layer spacing behavior. D' is preferably acovalent bond.

In general, the compounds of this invention have a central corecomprised of at least one or two rings independently selected from thegroup consisting of aromatic, heteroaromatic, alicyclic, substitutedaromatic, substituted heteroaromatic, and substituted alicyclic rings,the rings being connected one with another by a covalent bond or bychemical groups selected from the group consisting of --COO--, --COS--,--HC═N--, --CH═CH--, --C.tbd.C--, and --COSe--. The rings can be fusedor non-fused. The heteroatoms within the heteroaromatic rings compriseat least one atom selected from the group consisting of nitrogen,oxygen, and sulfur. Non-adjacent ring carbon atoms in the alicyclicrings can be substituted by nitrogen, oxygen, or sulfur atoms. When thering(s) are aromatic, heteroaromatic, substituted aromatic, orsubstituted heteroaromatic, the non-fused rings of the core arepreferably no more than about two in number.

When used in electrooptical display devices, the chiral liquid crystalcompounds of the invention provide exceptionally fast response timesover broad temperature ranges. The compounds exhibit surprisingly highpolarization values (relative to comparable compounds having a chiralcenter located on the other side of the core, away from thefluorochemical terminal portion) and surprisingly low viscosities inview of their high polarizations. In addition, many of the compoundshave broad smectic C. temperature ranges, making them useful alone, aswell as in admixture with other chiral or achiral liquid crystalcompounds (as dopants or as the major components), for electroopticaldisplay applications.

The compounds of the invention have a number of desirable propertieswhen used in admixture with other liquid crystal compounds, preferablycompounds having fluorinated terminal portions such as those compoundsdisclosed, for example, in U.S. Pat. No. 4,886,619 (Janulis), U.S. Pat.No. 5,082,587 (Janulis), and U.S. Pat. No. 5,262,082 (Janulis et al.).For example, the compounds of the invention when admixed with suchpreferred liquid crystal compounds show excellent compatibility, show abeneficial effect or only a minimal negative effect on the smectic C.temperature range of the resulting mixtures (even when present at highconcentrations), and provide ferroelectric mixtures having fastelectrical response times.

In other aspects, this invention also provides a mixture of liquidcrystal compounds comprising at least one liquid crystal compound of theinvention, a liquid crystal display device containing at least oneliquid crystal compound of the invention, liquid crystal intermediatecompounds, and a process for preparing the liquid crystal compounds ofthe invention.

DETAILED DESCRIPTION OF THE INVENTION

A class of the non-polymeric liquid crystal materials, i.e., liquidcrystal compounds, of the present invention can be represented by thegeneral formula I: ##STR2## where M, N, and P are each independentlyselected from the group consisting of ##STR3## a, b, and c are eachindependently zero or an integer of from 1 to 3, with the proviso thatthe sum of a+b+c be at least 1 (and preferably no greater than 2);

each A and B are non-directionally and independently selected from thegroup consisting of a covalent bond,

    --C(═O)--O--, --C(═O)--S--, --C(═O)--Se--,

--C(═O)--Te--, --(CH₂ CH₂)_(k) -- where k is 1 to 4, --CH═CH--,--C.tbd.C--, --CH═N--, --CH₂ --O--, --C(═O)--, and --O--;

each X, Y, and Z are independently selected from the group consisting of--H, --Cl, --F, --Br, --I, --OH, --OCH₃, --CH₃, --CF₃, --OCF₃, --CN, and--NO₂ ;

each l, m, and n are independently zero or an integer of 1 to 4;

D is non-directionally selected from the group consisting of a covalentbond, ##STR4## and combinations thereof, where r and r' areindependently integers of 0 to about 20, s is independently an integerof 1 to about 10 for each (C_(s) H_(2s) O), t is an integer of 1 toabout 6, and p is an integer of 0 to about 4;

R is selected from the group consisting of

    --O--((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q+1-v --(R').sub.v,

    --((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q+1-v --(R').sub.v,

    --C(═O)--O--C.sub.q H.sub.2q+1-v --(R').sub.v,

    --O--(O═)C--C.sub.q H.sub.2q+1-v --(R').sub.v, ##STR5## and

    --CR'H--(D).sub.g --CR'H--C.sub.q H.sub.2q+1-v --(R').sub.v,

where each R' is independently selected from the group consisting of--Cl, --F, -CF₃, --NO₂, --CN, --H, --H_(q) H_(2q+1),

--O--(O═)C--C_(q) H_(2q+1), --C(═O)--O--C_(q) H_(2q+1), --Br, --OH, and--OC_(q) H_(2q+1) (preferably, --H or --F); q' is independently aninteger of 1 to about 20 for each (C_(q') H_(2q') --O); q is an integerof 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0to about 6; each v' is independently an integer of 0 to about 6; g is aninteger of 1 to about 3; each D is independently and non-directionallyselected from the group set forth for D above, with the proviso that thering containing D has from about 3 to about 10 ring atoms; each W isindependently selected from the group consisting of N, CR', and SiR';and R can be chiral or achiral; and

R_(f) ' is --R*--D--(O)_(x) --CH₂ --D'--R_(f), where R* is a cyclic oracyclic chiral moiety; D and D' are each independently andnon-directionally selected from the group set forth for D above; x is aninteger of 0 or 1; and R_(f) is fluoroalkyl, perfluoroalkyl,fluoroether, or perfluoroether. Preferably, R_(f) is fluoroalkyl,fluoroether, or perfluoroether; and R* is selected from the groupconsisting of

    --O--((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q-v --(R').sub.v --,

    --((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q-v --(R').sub.v --,

    --C(═O)--O--C.sub.q H.sub.2q-v --(R').sub.v --,

    --O--(O═)C--C.sub.q H.sub.2q-v --(R').sub.v --, ##STR6## where each R' is independently selected from the group consisting of --Cl, --F, --Cf.sub.3, --NO.sub.2, --CN, --H, --C.sub.q H.sub.2q+1, --O--(O═)C--C.sub.q H.sub.2q+1, --C(═O)--O--C.sub.q H.sub.2q+1, --Br, --OH, and --OC.sub.q H.sub.2q+1, (preferably, --H, --F, --CF.sub.3, --Br, --OH, or --OCH.sub.3 ; more preferably, --H, --F, or --CF.sub.3); q' is independently an integer of 1 to about 20 for each ((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 0 to about 6; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms; and each W is independently selected from the group consisting of N, CR', and SiR'. More preferably, R.sub.f is perfluoroether. D' is preferably a covalent bond.

In defining R_(f), particularly preferred perfluoroalkyl groups arethose which can be represented by the formula --C_(q) F_(2q) X', where qis as defined above (and, preferably, is at least about 5) and X' ishydrogen or fluorine. Particularly preferred fluoroalkyl and fluoroethergroups are those which can be represented by the formula --R_(f)"--R_(h), where R_(f) " is a linear or branched, perfluorinated orpartially-fluorinated alkylene group having from 1 to about 10(preferably, from about 2 to about 6) carbon atoms and optionallycontaining one or more catenary, i.e., in-chain, ether oxygen atoms, andR_(h) is a linear or branched alkyl group having from 1 to about 14(preferably, from about 3 to about 10) carbon atoms and optionallycontaining one or more catenary ether oxygen atoms. Preferably, R_(f) "is perfluorinated, both R_(h) and R_(f) " are linear, and at least oneof the groups R_(h) and R_(f) " contains at least one catenary etheroxygen atom. More preferably, R_(h) or both R_(h) and R_(f) " containsat least one catenary ether oxygen atom.

Particularly preferred perfluoroether groups are those which can berepresented by the formula --(C_(x) F_(2x) O)_(z) C_(y) F_(2y+1), wherex is independently an integer of 1 to about 10 for each (C_(x) F_(2x)O), y is an integer of 1 to about 10, and z is an integer of 1 to about10. Preferably, the perfluoroether group is linear, x is independentlyan integer of 1 to about 6 for each (C_(x) F_(2x) O), y is an integer of1 to about 6, and z is an integer of 1 to about 6.

Preferred subclasses of the chiral compounds of the invention can berepresented by the following formula:

    R"--(O).sub.j --G--(OCH.sub.2).sub.j --R*--(C.sub.s H.sub.2s O).sub.t C.sub.r' H.sub.2r' --R.sub.f                              (II)

where R" is (R')_(v) --c_(q) H_(2q+1-v), where q is an integer of 2 toabout 10, each R' is independently selected from the group consisting ofhydrogen, fluorine, chlorine, methyl, and perfluoromethyl, and v is aninteger of 1 to about 3; j is an integer of 0 or 1; G is selected fromthe group consisting of ##STR7## R* is selected from the groupconsisting of --C_(q) H_(2q-v) --(R')_(v) -- and ##STR8## where R' is--F, q is an integer of 1 to about 4, v is an integer of 1 to about 3, Wis N or CH, and D is --C(═O)--O-- or --CH₂ --; s is an integer of 1 toabout 6; t is an integer of 0 or 1; r' is an integer of 1 to about 3;and R_(f) is selected from the group consisting of --C_(q) F_(2q) X',--R_(f) "R_(h), and --(C_(x) F_(2x) O)_(z) C_(y) F_(2y+1), where q is aninteger of 1 to about 6, X' is fluorine, R_(f) " is a linear orbranched, perfluorinated alkylene group having from about 2 to about 4carbon atoms and optionally containing one or more catenary ether oxygenatoms, R_(h) is a linear or branched alkyl group having from about 2 toabout 7 carbon atoms and optionally containing one or more catenaryether oxygen atoms, x is independently an integer of 1 to about 10 foreach (C_(x) F_(2x) O), y is an integer of 1 to about 8, and z is aninteger of 1 to about 5.

The fluorine-containing liquid crystal compounds of the invention can beprepared by a process comprising the steps of (a) mixing at least onecompound represented by the formula ##STR9## with at least one compoundrepresented by the formula ##STR10## or mixing at least one compoundrepresented by the formula ##STR11## with at least one compoundrepresented by the formula ##STR12## or mixing at least one compoundrepresented by the formula ##STR13## with at least one compoundrepresented by the formula ##STR14## where M, N, P, a, b, c, A, B, X, Y,Z, l , m, n, D, R, R*, R_(f), and R_(r) ' are as defined above forformula I; x is an integer of 0 or 1; and each A', A", B', and B" areindependently selected from the group consisting of --H, --Cl, --Br,--I, --OH, --COOH, --CH(CH₂ OH)₂, --SH, --SeH, --TeH, --NH₂, --COCl,--CHO, --OSO₂ R_(f) '", --OSO₂ CH₃, --NH(C═O)OC_(q) H_(2q+1), --NCO,--OSO₂ -cyclo(C₆ H₄)--CH₃, --CH₃ COOH, and --CH(C(O)O--C_(q) H_(2q+1))₂,where R_(f) '" is a perfluoroalkyl group having from 1 to about 10carbon atoms and q is an integer of 0 to about 20, and with the provisothat (R*)_(x) --A' can enter into an addition or condensation reactionwith A" and that (R*)_(x) --B' can enter into an addition orcondensation reaction with B"; and (b) allowing compounds III and IV,compounds V and VI, or compounds III and VII to react, optionally in thepresence of suitable coupling agent(s), i.e., reagent(s) which effectcoupling.

Most of the compounds of the present invention have enhanced smecticmesophases. Mixtures of the compounds of the invention with other liquidcrystal materials can be formulated to provide desired transitiontemperatures and broad mesophase temperature ranges. Such mixturespreferably contain compounds having fluorinated terminal portions, suchas those compounds described, for example, in U.S. Pat. No. 4,886,619(Janulis), U.S. Pat. No. 5,082,587 (Janulis), and, most preferably, U.S.Pat. No. 5,262,082 (Janulis et al.), the descriptions of which areincorporated herein by reference.

The compounds of this invention in admixture with other chiral orachiral liquid crystal compounds may exhibit chiral smectic liquidcrystal behavior. Furthermore, many of the perfluoroethergroup-containing liquid crystal compounds of the invention when usedalone or when mixed with other liquid crystal compounds of the inventionor with achiral, fluorine-containing liquid crystal compounds(preferably, the perfluoroether group-containing liquid crystalcompounds described in U.S. Pat. No. 5,262,082 (Janulis et al.)) exhibita reduced temperature dependence of the smectic interlayer spacing. Thisproperty provides for the spontaneous generation of a bookshelf typelayer structure, which is ideal for a ferroelectric liquid crystaldevice.

Another advantage of using the materials of this invention in theformulation of liquid crystal mixtures is the low birefringence whichcan be obtained. The low birefringence of the liquid crystal compoundsof the invention (relative to their nonfluorine-containing analoques)allows the fabrication of devices with larger device spacings. Lighttransmission through, e.g., a surface-stabilized ferroelectric device(as described in U.S. Pat. No. 4,367,924, the description of which isincorporated by reference herein) with two polarizers is represented bythe following equation:

    I=I.sub.o (sin.sup.2 (4Θ)) (sin.sup.2 (πΔnd/λ))

where

I_(o) =transmission through parallel polarizers

Θ=material tilt angle

Δn=liquid crystal birefringence

d=device spacing

λ=wavelength of light used

To maximize the transmission, both sin² (4Θ) and sin² (πΔnd/λ) must beat maximum. This occurs when each term equals one. The first term is amaximum when the tilt angle equals 22.5°. This is a function of theliquid crystal and is constant for a given material at a giventemperature. The second term is maximum when Δnd=λ/2. This demonstratesthe criticality of the low birefringence of the materials of thisinvention. Low birefringence allows a larger device thickness, d, for agiven wavelength of light. Thus, a larger device spacing is possiblewhile still maximizing transmission, allowing easier deviceconstruction.

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

In the following examples, all temperatures are in degrees Celsius andall parts and percentages are by weight unless indicated otherwise.Commercially available materials were chemically transformed by reactionpathways well-known to those skilled in the art and detailed in theexamples. Chemical transformations were comprised of acylation,esterification, etherification, alkylation, and combinations thereofusing fluorine-containing and nonfluorine-containing reactants toprovide the precursor compounds, which, in turn, were caused to reacttogether to yield the chiral, fluorine-containing liquid crystalcompounds of this invention.

Compounds prepared in the various examples of this invention werecharacterized by their melting or boiling point, and structures wereconfirmed by using at least one of the following methods of analysis:chromatography; ¹³ C--, ¹ H--, and ¹⁹ F-NMR; and infrared and massspectroscopies.

EXAMPLES

The 5-alkyl-2-(4-hydroxyphenyl)pyrimidines used in the examples wereprepared essentially as described by Zaschke and Stolle in "Syntheseniedrigschmelzender Kristallin-Flussiger Heterocyclen; 5-n-Alkyl-2-4-n-alkanoyloxy-phenyl!pyrimidine," Z. Chem. 15, 441-3 (1975). (S)- and(R)-2-fluoro-decyl-p-toluenesulfonate were prepared essentially asdescribed by Nohira et al. in Mol. Cryst. Liq. Cryst. 180B, 379 (1990).Fluorinated alcohols were prepared essentially as described in U.S. Pat.No. 5,262,082 (Janulis et al.; the description of which is incorporatedherein by reference) by sodium borohydride reduction of thecorresponding perfluorinated acids (or derivatives), which had beenprepared by electrochemical fluorination (ECF) or by direct fluorination(using elemental fluorine) of the corresponding hydrocarbon acids (orderivatives). See, e.g., the description of ECF given in U.S. Pat. No.2,519,983 (Simons), the description of which is incorporated herein byreference. Direct fluorination is described, e.g., in U.S. Pat. No.5,362,919 (Costello et al.), the description of which is alsoincorporated herein by reference.

Examples 1-35 describe procedures for preparing liquid crystal compoundsand liquid crystal intermediate compounds of this invention. Thechemical structure of each compound is given in Table 1.

Example 1 Preparation of 5-Octyl-2-4-((R)-2-fluoro-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyloxy)phenyl!pyrimidine

Dry nitrogen was bubbled through a solution of(S)-1,2-O-isopropylidine-3-butene-1,2-diol (1.0 g, 7.8 mmol) (preparedessentially by the procedure of Jajer et al. described in Synthesis1990, 556) and 1-iodo-perfluorohexane (3.48 g, 7.8 mmol) for 10 minutes.Tetrakis(triphenylphosphine)palladium(0) (90 mg, 0.078 mmol) was addedto the resulting mixture, and the mixture was stirred at roomtemperature for 10 hours. Tributyl tin hydride (2.1 ml, 7.8 mmol) wasthen added by syringe, and the mixture was stirred for an additional 10hours. The resulting product was distilled (44° C., 0.4 mm Hg) from themixture to give 2.5 g of(S)-1,2-O-isopropylidene-3-(perfluorohexyl)butane diol as a clearliquid. The dioxolane protecting group was then hydrolyzed to the diolby stirring the product in a solution of aqueous acidic tetrahydrofuranfor 4 hours. The resulting product was distilled under reduced pressure(80°-85° C., 0.4 mmHg) to give 2.1 g of(S)-2-hydroxy-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1-decanol. Theprimary alcohol was protected with trityl chloride (triphenylmethylchloride) essentially as described by Chaudhary et al. in TetrahedronLetters 1979, 95, and the resulting secondary alcohol was subsequentlytreated with diethylaminosulfur trifluoride (essentially as described byMiddleton in J. Org. Chem. 40, 574 (1975)) to givetriphenylmethoxy-(R)-2-fluoro-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecane.The trityl protecting group was then removed with aqueous acidictetrahydrofuran to give(R)-2-fluoro-5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-1-decanol. Thep-toluene sulfonate derivative of the alcohol was prepared by theaddition of 4-toluenesulfonyl chloride (120.6 mg, 0.63 mmol) to asolution of the alcohol (236 mg, 0.57 mmol), dimethylaminopyridine(DMAP, 2.8 mg, 0.02 mmol), and N,N'-diisopropylethylamine (0.2 ml, 1.14mmol) in dichloromethane (2.0 ml). The resulting mixture was stirred for8 hours at room temperature and was then coated onto 0.5 g of silicagel. The resulting product was then purified by eluting with 10:1hexanes/ethyl acetate on silica to give 280 mg of the sulfonate.

Sodium hydride (30 mg, 60 weight percent in oil, 6.6 mmol) was added toa stirred solution of 5-octyl-2-(4-hydroxyphenyl)pyrimidine (169 mg,0.59 mmol) and dimethyl formamide (2.0 ml). The resulting mixture wasstirred for 15 minutes under a nitrogen atmosphere, and then a solutionof the above-described sulfonate (280 mg, 0.496 mmol) in 2 ml ofdimethyl formamide was added by syringe. The mixture was heated to 60°C. for 4 hours and then cooled to ambient temperature. The mixture wasdiluted with water (5 ml) and extracted with three 10 ml aliquots ofdiethyl ether. The organic extract were collected, dried (over MgSO₄),filtered, and concentrated to give product in the form of a brown pastewhich solidified upon standing. The product was then purified by columnchromatography on silica gel (eluting with 10:1 hexanes/ethyl acetate)to give 233 mg of the title compound (having the structure shown inTable 1) as a white solid.

Example 2 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy)propoxy)phenyl!pyrimidine

(S)-2-hydroxy-3-(2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy)-propanolwas prepared by the following modification of a procedure described inU.S. Pat. No. 3,470,258 (Teroso et al.). (R)-glycidol (5.0 g, 67.5 mmol)was added dropwise to a 120° C. solution of2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanol (30 g, 101 mmol) andN,N'-diisopropylethylamine (0.47 ml, 2.7 mmol). The resulting mixturewas then stirred for one hour. The resulting product was distilled(79°-81° C. at 0.4 mm Hg) from the mixture to give 14.7 g of(S)-2-hydroxy-3-(2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy)-1-propanolas a clear liquid.(R)-2-fluoro-3-(2,2,3,3,4,4,5,5,6,6,6-undecafluorohexane-1-p-toluenesulfonatewas then prepared using essentially the procedure described in Example1.

Sodium hydride (0.223 g, 9.3 mmol) was added to a stirred solution ofthe sulfonate (3.00 g, 5.65 mmol) and5-octyl-2-(4-hydroxyphenyl)pyrimidine (1.77 g, 6.2 mmoles) usingessentially the procedure described in Example 1 to give the titlecompound.

Example 3 Preparation of 5-Octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

A solution of potassium hydroxide (1.97 g, 35 mmol) in water (1.97 ml)was added to a solution of (R)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (10.0 g, 29.3 mmol) (preparedessentially as described by Sakaguchi et al. in Ferroelectrics 114, 269(1992)), 2,2-difluoro-2- 1,1,2,2-tetrafluoro-2-nonfluorobutoxy)ethanol!(15.2 g, 35.16 mmol), and tetrabutyl ammonium hydrogen sulfate (500 mg,1.5 mmol) in tetrahydrofuran (20 ml). The resulting mixture was heatedto reflux temperature for 23 hours, was diluted with water (100 ml), andwas extracted with three 100 ml aliquots of ethyl acetate. The organicextracts were concentrated under reduced pressure, and the resultingproduct was recrystallized from acetonitrile (150 ml) to give -2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)1,1,2,2-tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!-5-octyl-pyrimidineas a white solid.

Example 4 Preparation of 5-Octyl-2-4-((S)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

A solution of 5-octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(prepared essentially as in Example 3, 8.0 g, 10.35 mmol) in drytetrahydrofuran (50 ml) was added dropwise to a -70° C. solution ofdiethylaminosulfur trifluoride (3.3 g, 20.7 mmol) in tetrahydrofuran (50ml). The resulting mixture was warmed to -30° C. over a period of 2hours, and then pyridine (3.3 g, 41.4 mmol) was added to the mixture.The mixture was allowed to warm to ambient temperature and was stirredfor 12 hours. The mixture was then poured into a slurry of silica gel(40 g) in diethyl ether and was concentrated onto the silica gel underreduced pressure. The product-coated silica was placed on top of 100 gof fresh silica gel and was eluted with a 10:1 hexanes/ethyl acetatesolution. Fractions collected containing the product were concentratedunder reduced pressure. The product was then recrystallized frommethanol to give 4.9 g of the title compound as a white solid.

Example 5 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Example 4using 5-octyl-2-4-((S)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidinein place of 5-octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine.

Example 6 Preparation of 5-Octyl-2-4-((S)-2-bromo-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

Perfluorobutanesulfonyl fluoride (389 mg, 1.29 mmol) was added dropwiseto a --20° C. solution of 5-octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine (Example 4, 1.0 g, 1.29 mmol)and diisopropyl ethylamine (334 mg, 2.58 mmol) in tetrahydrofuran (2ml). Tetrabutylammonium bromide (416 mg, 1.29 mmol) was then added tothe resulting mixture, and the mixture was allowed to warm to ambienttemperature. The mixture was stirred at ambient temperature for 5 hours.The mixture was coated on to silica gel, and the resulting product wasthen purified by column chromatography (eluting with 10:1 hexanes/ethylacetate) followed by recrystallization from methanol.

Example 7 Preparation of 5-Octyl-2-4-((R)-2-methoxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

Methyl iodide (1.1 g, 7.76 mmol) was added to a solution of 5-octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 4, 1.5 g, 1.94 mmol) and sodium hydride (116 mg, 60 weightpercent in oil, 2.91 mmol) in dimethyl formamide (10 ml). The resultingmixture was stirred at room temperature for 10 hours, was diluted with50 ml of water, and was extracted with three 50 ml aliquots of diethylether. The organic extracts were dried (over MgSO₄), filtered, andconcentrated. The resulting product was then recrystallized frommethanol at -30° C. to give a white smectic material.

Example 8 Preparation of 5-Hexyl-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

A solution of 5-hexyl-2-(4-hydroxyphenyl)pyrimidine (1.0 g, 4.08 mmol),3-(2-2-(nonafluorobutoxy)tetrafluoroethoxy!-2,2-difluoroethoxy)-(R)-2-fluoropropyl-1-p-toluenesulfonate(2.7 g, 4.08 mmol, prepared essentially as described in Example 2 byreplacing 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanol with 2-2-(nonafluorobutoxy)tetrafluoroethoxy!-2,2-difluoro-1-ethanol), andpotassium carbonate (0.62 g, 4.5 mmol) in acetonitrile (30 ml) washeated to reflux temperature and maintained at that temperature for 16hours. The resulting mixture was then coated onto silica gel, and theresulting product was purified by column chromatography and subsequentrecrystallization from methanol.

Example 9 Preparation of 5-Hexyloxy-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

2-Hexyloxyacetaldehyde diethylacetal was prepared as follows:

Hexanol (200 g, 1.96 mol) and toluene (600 ml) were added to a 3 literflask fitted with a mechanical stirrer and a reflux condenser. Sodiumhydride (51.6 g, 2.15 mol) was added slowly to the resulting mixture,and then bromoacetaldehyde diethylacetal (385.7 g, 1.96 mol) was addeddropwise. The mixture was heated to reflux temperature and maintained atthat temperature for 6 hours. The mixture was then cooled to ambienttemperature and was filtered to remove the resulting solids. Toluene wasremoved from the filtrate under reduced pressure, and the resultingproduct was distilled (85°-88° C.) to give 189.4 g of2-hexyloxyacetaldehyde diethylacetal.

5-Hexyloxy-2-(4-hydroxyphenyl)pyrimidine was prepared essentially by theprocedure described by Zaschke et al., supra. The title compound wasthen prepared essentially as described in Example 8 by replacing5-hexyl-2-(4-hydroxyphenyl)pyrimidine with5-hexyloxy-2-(4-hydroxyphenyl)pyrimidine (0.54 g, 2.0 mmol.

Example 10 Preparation of 5-Octyloxy-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

5-Octyloxy-2-(4-hydroxyphenyl)pyrimidine was prepared essentially asdescribed in Example 9 by substituting octanol for hexanol. The titlecompound was then prepared essentially as described in Examples 3 and 4by replacing (R)-5-octyl-2- 4-(2,3-oxiranylpropoxy)phenyl!pyrimidinewith (S)-5-octyloxy-2- 4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (10.0 g,28.0 mmol) and using 2-2-(nonfluorobutoxy)tetrafluoroethoxy!-2,2-difluoroethanol (13.3 g, 31mmol). The resulting (S)-hydroxy compound was treated with 2 equivalentsof diethylaminosulfur trifluoride to produce the title compound.

Example 11 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(2-(2-(2-(trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining2-(2-(2-(trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)-2,2-difluoro-1-ethanol(2.8 g, 7.0 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.87 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(2-(2-(2-(trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine.This chiral (S)-hydroxy compound (2.95 g, 4.0 mmol) was treated withdiethylaminosulfur trifluoride (1.29 g, 8.0 mmol) to produce the titlecompound.

Example 12 Preparation of 5-Octyl-2-4-((S)-2-fluoro-3-(4-(nonafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)propoxy)phenyl!pyrimidine

(R)-Benzylglycidyl ether (2.0 g, 12.2 mmol, prepared essentially asdescribed by Byun et al. in Tet. Lett. 30, 2751 (1989)) was addeddropwise to a 120° C. solution of potassium carbonate (0.17 g, 1.2 mmol)in 4-nonafluorobutoxy-2,2,3,3,4,4-hexafluoro-1-butanol (5.1 g,12.2mmol). The resulting mixture was stirred for 3 hours at 120° C. andwas then cooled to ambient temperature and distilled (0.6 torr,110°-130° C.) to give 6.25 g of1-benzyloxy-(R)-2-hydroxy-3-(4-(nonafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)propane.

This product was then converted to1-benzyloxy-(S)-2-fluoro-3-(4-nonafluorobutoxy-2,2,3,3,4,4-hexafluorobutoxy)propaneby essentially the procedure described in Example 4. Removal of thebenzyl protecting group was effected by hydrogenation (3100 torr (60psi) H₂ and a catalytic amount of 10% Pd on carbon in tetrahydrofuran)to give(S)-2-fluoro-3-(4-nonafluorobutoxy-2,2,3,3,4,4-hexafluorobutoxy)-1-propanol.

(S)-2-fluoro-3-(4-(nonafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)propyl-1-p-toluenesulfonatewas prepared essentially as described in Example 1. The title compoundwas then prepared essentially as described in Example 8 using5-octyl-2-(4-hydroxyphenyl)pyrimidine (1.5 g, 5.28 mmol) and(S)-2-fluoro-3-(4-(nonafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)propyl-1-p-toluenesulfonate(3.1 g, 4.8 mmol).

Example 13 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(10-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluorodecyloxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining10-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluoro-1-decanol(5.8 g, 7.0 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.87 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(10-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluorodecyloxy)propoxy)phenyl!pyrimidine.This chiral (S)-hydroxy compound (3.6 g, 3.1 mmol) was treated withdiethylaminosulfur trifluoride (1.0 g, 6.2 mmol) to produce the titlecompound.

Example 14 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(5-butoxy-2,2,3,3,4,4-hexafluoropentoxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining 5-butoxy-2,2,3,3,4,4-hexafluoropentanol (3.1 g, 11.7mmol, prepared essentially by the method described in U.S. Pat. No.5,399,291 (Janulis et al.)) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.87 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(-5-butoxy-2,2,3,3,4,4-hexafluoropentoxy)propoxy)phenyl!pyrimidine.This chiral (S)-hydroxy compound (2.0 g, 3.3 mmol) was treated withdiethylaminosulfur trifluoride (1.06 g, 6.6 mmol) to produce the titlecompound.

Example 15 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(2-(N-(2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2-difluoroethoxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining2-(N-(2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2-difluoroethanol (2.18g, 7.0 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.87 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(2-(N-(2,2,3,3,5,5,6,6-octafluoro)morpholino)-2,2-difluoroethoxy)propoxy)phenyl!pyrimidine.This chiral (S)-hydroxy compound (3.0 g, 4.6 mmol) was treated withdiethylaminosulfur trifluoride (1.5 g, 9.2 mmol) to produce the titlecompound.

Example 16 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(2-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)ethoxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining2-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)ethanol(3.3 g, 7.0 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.87 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(2-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)ethoxy)propoxy)phenyl!pyrimidine.This chiral (S)-hydroxy compound (1.6 g, 1.95 mmol) was treated withdiethylaminosulfur trifluoride (0.63 g, 3.92 mmol) to produce the titlecompound.

Example 17 Preparation of(R)-2,3-Difluoro-4-octyl-4'-(2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)1,1'-biphenyl

The title compound was prepared essentially as described in Example 8 bycombining 3-(2-2-(nonfluorobutoxy)tetrafluoroethoxy!-2,2-difluoroethoxy)-(R)-2-fluoropropyl-1-p-toluenesulfonate(0.5 g, 0.75 mmol) with 2,3-difluoro-4-octyl-4'-hydroxybiphenyl (0.24 g,0.75 mmol, prepared essentially as described by Gray et al. in J. Chem.Soc., Perkin Trans. II 1989, 2041).

Example 18 Preparation of 5-((R)-2-Fluorodecyloxy)-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

5-Benzyloxy-2-(4-hydroxy)phenyl!pyrimidine was prepared essentially asdescribed in Example 9 by replacing benzyl alcohol for hexanol.5-Benzyloxy-2-(4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)propoxy)phenyl!pyrimidinewas prepared essentially as described in Example 8 using5-benzyloxy-2-(4-hydroxy)phenyl!pyrimidine (0.97 g, 3.47 mmol) in placeof 5-hexyl-2-(4-hydroxyphenyl)pyrimidine. The benzyl protecting groupwas removed by hydrogenation using 10% Pd on carbon in tetrahydrofuranunder 3100 torr (60 psi) hydrogen pressure until the reaction was shownto be complete by thin layer chromatography. The Pd catalyst was removedby filtration, and the solvent was removed under reduced pressure togive5-hydroxy-2-(4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)propoxy)phenyl!pyrimidineas a white solid. This hydroxyphenylpyrimidine (760 mg, 1.12 mmol),(R)-2-fluoro-decyl-p-toluenesulfonate (370 mg, 1.12 mmol), and potassiumcarbonate (150 mg, 1.12 mmol) in acetonitrile (30 ml) were stirred atreflux temperature until the reaction was shown to be complete by gaschromatography. The resulting product was then coated onto silica gel (2g) and was purified by column chromatography (eluting with 15:1hexane/ethyl acetate) to give 695 mg of the title compound as a whitesolid. The solid was further purified by recrystallization frommethanol.

Example 19 Preparation of 5-((S)-2-Fluorodecyloxy)-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Example 18using (S)-2-fluoro-decyl-p-toluenesulfonate (0.146 g, 0.44 mol) in placeof (R)-2-fluoro-decyl-p-toluenesulfonate.

Example 20 Preparation ofN-(4-Octyloxy)phenyl-(S)-5-((2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)methyl-2-oxazolidinone

A one liter flask, equipped with a dropping addition funnel, amechanical stirrer, a thermometer, and a reflux condenser was chargedwith (R)-epichlorohydrin (5 g, 0.54 mol) under positive nitrogenpressure and was heated to 75° C. A mixture of2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethanol (22.8 g, 53mmol) and potassium-t-butoxide (53 mL of 1M in t-butanol) was added tothe flask over a period of 1.5 hours, with stirring. The flask was thencooled to ambient temperature and the contents distilled to yield(S)-2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethyl-glycidylether (8.8 g, b.p. 65° C. at 0.3 torr).

A solution of N-(4-benzyloxy)phenylethyl urethane (1.0 g, 3.68 mmol,prepared essentially as described by Iwakura et al. in J. Org. Chem. 29,379 (1964)),(S)-2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethyl-glycidylether (1.8 g, 3.68 mmol), and triethyl amine (370 mg, 3.68 mmol) intetrahydrofuran (5 ml) was heated to reflux temperature for 48 hours.The resulting product was coated onto silica gel and was purified bycolumn chromatography (eluting with 20:1 toluene/ethyl acetate) to give1.6 of a tan solid. The solid was dissolved in tetrahydrofuran (10 ml),and the resulting solution was stirred for 24 hours in the presence of10% Pd on carbon (100 mg) under 3100 torr (60 psi) of hydrogen. The Pdcatalyst was removed by filtration, and the filtrate was concentratedunder reduced pressure to give 1.25 g ofN-(4-hydroxy)phenyl-(S)-5-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)methyl-2-oxazolidinoneas a white solid.

A solution of of this oxazolidinone (250 mg, 0.4 mmol), 1-bromooctane(116 mg, 0.6 mmol), and potassium carbonate (83 mg, 0.6 mmol) inacetonitrile (20 ml) was stirred at reflux temperature for 18 hours. Theresulting product was coated on to silica gel (2 g) and was purified bycolumn chromatography to give 370 mg of the title compound. The compoundwas further purified by recrystallization from methanol.

Example 21 Preparation ofN-(4-Octyloxybenzoy1)phenyl-(S)-5-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethoxy)methyl-2-oxazolidinone

Triethylamine (230 mg, 1.76 mmol) was added to a solution ofN-(4-hydroxy)phenyl-(S)-5-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethoxy)methyl-2-oxazolidinone(500 mg, 0.88 mmol) and 4-octyloxybenzoyl chloride (220 mg, 0.88 mmol)in dichloromethane (10 ml). The resulting mixture was stirred at ambienttemperature for 4 hours and was then coated onto silica gel and theresulting product purified by column chromatography. The product wasfurther purified by recrystallization from methanol to give 533 mg ofthe product as a white solid.

Example 22 Preparation of 5-Octyl-2-(4-(S)-5-oxymethyl-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)-2(3H)furanone)phenyl!pyrimidine

A one liter flask was fitted with an addition funnel, a mechanicalstirrer, a reflux condenser, and a thermometer and was charged with1,3-dibromopropane (360 g, 1.78 mol),2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethanol (150 g,0.347 mol), and Adogen 464™ quaternary ammonium phase transfer catalyst(available from Aldrich Chemical, 30 g). The resulting mixture washeated to 70° C., and the mixture was maintained at 70°-90° C. whilepotassium hydroxide (84 g, 1.5 mol, dissolved in 50 mL water) was addeddropwise with stirring. After complete addition, the mixture wasmaintained at 70°-80° C. for one hour, was cooled, and then water (300mL) was added. The resulting upper aqueous layer of the mixture wasdiscarded, and perfluorohexane was added to the remainder. Excessdibromopropane was decanted from the resulting mixture, and theremaining volatile components of the mixture were removed under reducedpressure. The resulting product,3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)-1-bromopropane,was purified by distillation on a six-plate Snyder column (b.p. 48°-52°C. at 0.05 torr).

A flask was then charged with dry dimethyl formamide and sodium hydride(1.3 g, 43.3 mmol, 80 weight percent dispersion in oil) under positivenitrogen pressure, followed by dropwise addition of diethyl malonate(7.1 g, 44 mmol) with stirring. When gas evolution ceased, C₄ F₉ OC₂ F₄OCF₂ CH₂ OC₃ H₆ Br (25 g, 40.6 mmol) was added to the flask, and theresulting mixture was heated to 85° C. and then stirred at ambienttemperature overnight. The resulting lower fluorochemical phase of themixture was separated, and the upper phase was treated with ether (60mL) and water (40 mL) and then washed with brine. The resulting etherphase was added to the fluorochemical phase. The volatile components ofthis combined fluorochemical phase were removed under reduced pressureat 40° C., and then the product, C₄ F₉ OC₂ F₄ OCF₂ CH₂ OC₃ H₆ CH(CO₂ C₂H₅)₂, was purified by distillation (b.p. 86°-90° C. at 0.05 torr).

A flask was then charged with the malonate product (4 g, 6.3 mmol),5-octyl-2-((4-oxymethyl-(S)-2-oxiranyl)phenyl)pyrimidine (2.2 g, 6.8mmol), potassium-t-butoxide (6.8 mL of 1M), and t-butanol (15 mL) andwas then heated at 83°-87° C. for 4 hours with stirring. The resultingmixture was acidified with 4.5% aqueous HCl and was stirred at 0° C. for30 minutes. The resulting yellow, gummy solid product was removed byfiltration and was air-dried. The product was further purified byrecrystallization from methanol. The cis(S,S) isomer of the product wasisolated as a 4.9:1 ratio of the cis to trans, and the trans(S,R) isomerwas isolated as a 7.3:1 ratio of the trans to cis isomers by liquidchromatography on silica gel using 4:1 hexanes/ethyl acetate as theeluent.

Examples 23 and 24 Preparation of 5-Octyl-2-4-((S)-2-hydroxy-3-(4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethoxy)phenyl)propoxy)phenyl!pyrimidineand 5-Octyl-2-4-((R)-2-fluoro-3-(4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethoxy)phenyl)propoxy)phenyl!pyrimidine

Example 23 was prepared essentially as described in Examples 3 and 4 bycombination of4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenol(1.4 g, 2.9 mmol, prepared essentially as described in U.S. Pat. No.5,262,082 (Janulis et al.)) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (1.0 g, 2.9 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethoxy)phenyl)propoxy)phenyl!pyrimidine(Example 23). This chiral (S)-hydroxy compound (1.5 g, 1.7 mmol) wastreated with diethylaminosulfur trifluoride (0.6 g, 3.5 mmol) to produceExample 24.

Examples 25 and 26 Preparation of 5-Octyl-2-4-((S)-2-hydroxy-3-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexylyloxy)propoxy)phenyl!pyrimidineand 5-Octyl-2-4-((R)-2-fluoro-3-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexylyloxy)propoxy)phenyl!pyrimidine

The title compounds were prepared essentially as described in Examples 3and 4 by combining6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol(22.2 g, 35 mmol) with (S)-5-octyl-2- 4-(2,3-5oxiranylpropoxy)phenyl!pyrimidine (10.0 g, 29.4 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)propoxy)phenyl!pyrimidine(Example 25). This chiral (S)-hydroxy compound (20 g, 21 mmol) wastreated with diethylaminosulfur trifluoride (6.6 g, 41 mmol) to produceExample 26. The structures of the compounds are shown in Table 1.

Examples 27 and 28 Preparation of 5-Octyl-2-4-((S)-2-hydroxy-3-(4-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4-hexafluorobutyloxy)propoxy)phenyl!pyrimidineand 5-Octyl-2-4-((R)-2-fluoro-3-(4-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4-hexafluorobutyloxy)propoxy)phenyl!pyrimidine

The title compounds were prepared essentially as described in Examples 3and 4 by combining4-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4-hexafluoro-1-butanol(3.7 g, 7 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.87 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(4-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4-hexafluorobutyloxy)propoxy)phenyl!pyrimidine(Example 27). This chiral (S)-hydroxy compound (3 g, 3.4 mmol) wastreated with diethylaminosulfur trifluoride (1.1 g, 6.8 mmol) to produceExample 28. The structures of the compounds are shown in Table 1.

Examples 29 and 30 Preparation of 5-Octyl-2-6-((S)-2-hydroxy-3-(6-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)propoxy)phenyl!pyrimidineand 5-Octyl-2-6-((R)-2-fluoro-3-(6-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)propoxy)phenyl!pyrimidine

The title compounds were prepared essentially as described in Examples 3and 4 by combining6-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy-2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol(11.5 g, 15.4 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (5.0 g, 15.34 mmol) to produce5-octyl-2-4-((S)-2-hydroxy-3-(6-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)tetrafluoroethoxy-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)propoxy)phenyl!pyrimidine(Example 29). This chiral (S)-hydroxy compound (10.0 g, 9.2 mmol) wastreated with diethylaminosulfur trifluoride (5.8 g, 36 mmol) to produceExample 30. The structures of the compounds are shown in Table 1.

Examples 31 and 32 Preparation of 5-Octyl-2-4-((S)-2-hydroxy-3-(2,2,2-trifluoroethoxy)propoxy)phenyl!pyrimidine and5-Octyl-2-4-((R)-2-fluoro-3-(2,2,2-trifluoroethoxy)propoxy)phenyl!pyrimidine

The title compounds were prepared essentially as described in Examples 3and 4 by combining 2,2,2-trifluoroethanol (1.1 g, 11.2 mmol) with(S)-5-octyl-2- 4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.0 g, 5.6mmol) to produce 5-octyl-2-4-((S)-2-hydroxy-3-(2,2,2-trifluoroethoxy)propoxy)phenyl!pyrimidine(Example 31). This chiral (S)-hydroxy compound (2.0 g, 4.5 mmol) wastreated with diethylaminosulfur trifluoride (1.46 g, 9.0 mmol) toproduce Example 32. The structures of the compounds are shown in Table1.

Example 33 Preparation of (S)-5-Octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)methyl-2-oxazolidinone)phenyl!pyrimidine

5-Octyl-2-(4-aminophenyl)pyrimidine was prepared by the followingmodification of the procedure described by Zaschke et al. in Z. Chem.15, 441 (1975). Sodium methoxide (25% in methanol, 79.7 g, 3.07 eq) wasadded to a solution of 4-amino benzamidine hydrochloride (25 g) and2-octyl-3-dimethylamino acrolein (25.7 g, 1.0 eq) in methanol (400 ml).The resulting mixture was heated to reflux temperature for 18 hours andwas then cooled to ambient temperature. The mixture was acidified withconcentrated HCl and was then filtered. The filtrate was diluted with400 ml of water and was extracted with three 200 ml aliquots of toluene.The combined extracts were concentrated, dissolved in 400 ml ofmethanol, filtered, and made strongly acidic by saturation with gaseousHCl. Removal of the solvent provided a red oil which was treated with250 ml of hot acetone and allowed to cool. Filtration gave 7.5 g of thecrude HCl salt. The salt (1 g) was neutralized with 5 equivalents oftriethylamine in tetrahydrofuran (10 ml), and the resulting free aminewas purified by liquid chromatography on silica gel using 20:1dichloromethane/ethyl acetate as the eluent.

A solution of the free amine (5-octyl-2-(4-aminophenyl)pyrimidine, 0.37g, 1.31 mmol) in acetonitrile (2 ml) was added dropwise to a solution ofmagnesium perchlorate (0.29 g, 1.31 mmol) and2-(2-(nonafluorobutoxy)tetrafluoroethoxy)ethyl-glycidyl ether (0.64 g,1.31 mmol) in acetonitrile (1 ml). The resulting mixture was stirredunder a nitrogen atmosphere for 18 hours, during which time a whiteprecipitate formed. The precipitate was isolated by filtration to give0.88 g of crude amino alcohol(5-octyl-2-(4-(3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy-2-hydroxypropyl)aminophenyl)pyrimidine).A solution of triphosgene (96 mg, 0.33 mmol) in dichloromethane (2 ml)was then added dropwise to a 0° C. solution of the amino alcohol (500mg, 0.56 mmol) and pyridine (0.26 ml, 3.25 mmol) in dichloromethane (4ml). The resulting mixture was stirred for 1 hour at 0° C. and then for3 hours at ambient temperature. The mixture was then coated onto silicagel and purified by chromatography on silica gel using 15:1dichloromethane/ethyl acetate as the eluent. The resulting product wasfurther purified by recrystallization from hexane.

Example 34 Preparation of 5-Octyl-2-4-((S)-2-hydroxy-3-(8-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyloxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining8-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1-octanol(6.4 g, 8.8 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (2.5 g, 7.35 mmol).

Example 35 Preparation of 5-Octyl-2-4-((S)-2-hydroxy-3-(4-(2-(tridecafluorohexyloxy)tetrafluoroethoxy)-2,2,3,3,4,4-hexafluorobutyloxy)propoxy)phenyl!pyrimidine

The title compound was prepared essentially as described in Examples 3and 4 by combining4-(2-(tridecafluorohexyloxy)tetrafluoroethoxy)-2,2,3,3,4,4-hexafluorobutanol(6.4 g, 10.1 mmol) with (S)-5-octyl-2-4-(2,3-oxiranylpropoxy)phenyl!pyrimidine (4.0 g, 11.8 mmol).

Comparative Example 1 Preparation of 5-Octyl-2-4-((R)-2-fluoro-3-(2-(2-butoxyethoxy)ethoxy)propoxy)phenyl!pyrimidine

Boron trifluoride etherate (1.3 ml, 10.8 mmol) was added dropwise to a0° C. solution of 2-(2-butoxyethoxy)ethanol (35 g, 216 mmol) and(S)-epichlorohydrin (10 g, 108 mmol). The resulting mixture was warmedslowly to ambient temperature and was stirred for 18 hours at ambienttemperature. 1-chloro-3-(2-(2-butoxyethoxy)ethoxy)-2-propanol wasdistilled from the mixture (105°-110° C. at 0.3 torr).

Potassium carbonate (2.1 g, 15.7 mmol) was added to a solution of5-octyl-2-(4-hydroxyphenyl)pyrimidine (3.0 g, 10.5 mmol) and1-chloro-3-(2-(2-butoxyethoxy)ethoxy)-2-propanol (2.7 g, 10.5 mmol) inN,N-dimethylformamide (100 ml). The resulting mixture was stirred atreflux temperature for 18 hours and then cooled to ambient temperature.The mixture was diluted with water (100 ml) and was extracted with three100 ml aliquots of diethyl ether. The extracts were dried (over MgSO₄),filtered, and concentrated to give crude product as an oil. 5-Octyl-2-4-((S)-2-hydroxy-3-(2-(2-(butoxy)ethoxy)ethoxy)propoxy)phenyl!pyrimidinewas then isolated by chromatography. The chiral (S)-hydroxy compound(3.5 g, 7.5 mmol) was treated with diethylaminosulfur trifluoride (5.3g, 15 mmol) to produce Comparative Example 1.

                                      TABLE 1                                     __________________________________________________________________________    Example No.                                                                              Structure                                                          __________________________________________________________________________     1                                                                                        ##STR15##                                                          2                                                                                        ##STR16##                                                          3                                                                                        ##STR17##                                                          4                                                                                        ##STR18##                                                          5                                                                                        ##STR19##                                                          6                                                                                        ##STR20##                                                          7                                                                                        ##STR21##                                                          8                                                                                        ##STR22##                                                          9                                                                                        ##STR23##                                                         10                                                                                        ##STR24##                                                         11                                                                                        ##STR25##                                                         12                                                                                        ##STR26##                                                         13                                                                                        ##STR27##                                                         14                                                                                        ##STR28##                                                         15                                                                                        ##STR29##                                                         16                                                                                        ##STR30##                                                         17                                                                                        ##STR31##                                                         18                                                                                        ##STR32##                                                         19                                                                                        ##STR33##                                                         20                                                                                        ##STR34##                                                         21                                                                                        ##STR35##                                                         22                                                                                        ##STR36##                                                         22 CIS                                                                                    ##STR37##                                                         22 TRANS                                                                                  ##STR38##                                                         23                                                                                        ##STR39##                                                         24                                                                                        ##STR40##                                                         25                                                                                        ##STR41##                                                         26                                                                                        ##STR42##                                                         27                                                                                        ##STR43##                                                         28                                                                                        ##STR44##                                                         29                                                                                        ##STR45##                                                         30                                                                                        ##STR46##                                                         31                                                                                        ##STR47##                                                         32                                                                                        ##STR48##                                                         33                                                                                        ##STR49##                                                         34                                                                                        ##STR50##                                                         35                                                                                        ##STR51##                                                         Comparative Example 1                                                                     ##STR52##                                                         __________________________________________________________________________

The compounds of Table 1 were evaluated for transition temperatures bydifferential scanning calorimetry (DSC) and/or optical observation ofmaterial phase changes using a Linkham TMH600 hot stage and a polarizingmicroscope. The transition temperatures (°C.) were obtained upon coolingthrough the isotropic state (I) to the smectic A mesophase (S_(A)), thesmectic C. mesophase (S_(C)), and higher order mesophases (M1 and M2)and are set forth in Table 2 below.

                  TABLE 2                                                         ______________________________________                                                                             S.sub.M to                                                                    S.sub.C, S.sub.A,                        Example No.                                                                           I to S.sub.A                                                                          to S.sub.C                                                                            to S.sub.M1                                                                         to S.sub.M2 /K                                                                       or I                                     ______________________________________                                         1      128.9   --      --    90.8   103                                       2      84.4    --      --    69.5   90.2                                      3      73.5    70.5    --    24.2   52.9                                      4      93      64.2    --    -10.4  40.1                                      5      93      64.21   --    -12.1  39.9                                      6      49.9    48.7    --    45.8   51                                        7      73.7    --      --    -31.8  9.7                                       8      90.7    49.3    --    20.9   39.7                                      9      121.1   98.0    --    24.0   44.6                                     10      117.4   101.8   --    6.1    46.3                                     11      89.7    57.1    --    -12.7  33.3                                     12      94      65.9    --    3.5    44.1                                     13      136     105     --    69.9   82.8                                     14      --      --      --    --     69.6                                     15      53.0    --      --    -19.2  34.1                                     16      76.0    --      --    -25    -9.6                                     17      28.2    --      --    -19.4  -1.45                                    18      106.7   89.7    --    63.23  65.9                                     19      102.7   83.7    59.5  48.6   67.5                                     20      45.1    --      --    32.1   53.9                                     21      152.7   --      --    69.6   83.3                                     22      99.1    57.3    --    <-14   >21                                      22 cis  95.8    --      --    58.6   79.3                                     22 trans                                                                              98.8    --      --    42.6   70.4                                     24      83.7    --      --    72.4   90.9                                     26      113.5   86.9    --    23.5   39.9                                     28      99.5    68.6    32.6  -1.4   36.1                                     30      115.9   86.3    --    25.0   43.0                                     32      --      --      --    --     mp = 88-89° C.                    33      140     --      --    128    138                                      Compar- --      --      --    <20° C.                                                                       --                                       ative 1                                                                       ______________________________________                                    

The data in Table 2 shows that most of the compounds of the inventionexhibit smectic mesophases and that many of the compounds exhibit abroad smectic C. mesophase, which makes the compounds well-suited foruse in liquid crystal display devices. As a result of the breadth of thesmectic C. mesophase, the compounds are useful in admixture withthemselves or with other liquid crystal compounds, even at highconcentration. In contrast with Example 5 which shows a broad smectic C.mesophase, Comparative Example 1 shows no liquid crystal behavior above20° C.

Examples 36-53 describe liquid crystal compound mixtures and/or liquidcrystal display devices of the invention.

Example 36

A device containing a chiral compound of this invention (Example 5) wasprepared essentially as described in U.S. Pat. No. 5,377,033 (Radcliffe)and filled with a mixture of 9.7 weight percent 5-octyl-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 5), 11.5 weight percent 5-octyloxy-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine(prepared essentially as described in U.S. Pat. No. 5,262,082 (Januliset al.)), 11.6 weight percent 5-decyloxy-2-4-(4-(nonafluorobutoxy)octafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)phenyl!pyrimidine,12.6 weight percent 5-decyloxy-2-2-(2-(tridecafluorohexyloxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine,6.6 weight percent 5-octyl-2-4-(3-(4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)2,2-difluoroethoxy)phenyl)phenyl!pyrimidine,13.4 weight percent 5-octyl-2-4-(4-(nonafluorobutoxy)octafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)phenyl!pyrimidine,and 34.7 weight percent 5-decyl-2-4-(4-(nonafluorobutoxy)octafluorobutoxy)-2,2,3,3,4,4-hexafluorobutoxy)phenyl!pyrimidine.

The ITO-constituted electrodes of the device were connected to anarbitrary waveform generator with variable output voltage. The devicewas driven by a voltage waveform consisting of bipolar, square pulses of±10V/μm amplitude, spaced 30 milliseconds apart by a train of squarepulses having the same width and 3.3 V/μm amplitude. The device washeated to the temperatures noted in Table 3 (below) and the polarization(nC/cm²), the τ_(electric), the smectic viscosity, and the tilt angleφ_(t) were determined as described below:

The polarization of the device was determined essentially as describedby Miyasato et al. in Jap. J. Appl. Phys. 22, 661 (1983). The electronicresponse time, τ_(electric), was derived from the displacement currentof the ferroelectric liquid crystal device under an applied squarevoltage pulse. The current was viewed on a 100 megahertz bandwidthoscilloscope. The usual decaying exponential, associated with adielectric filled capacitor, was followed by the spontaneouspolarization (P_(s)) switching pulse. The time from the rising edge ofthe voltage pulse to the peak of the P_(s) pulse was taken to beτ_(electric). The rotational viscosity (smectic viscosity, η) wascalculated as shown below:

    η(10.sup.-3 kg/m·s)=0.01·Ps·E·τ.sub.electric,

where the units of P_(s), E, and τ_(electric) are respectively nC/cm² ,V/μm, and μs. The tilt angle φ_(t) of the mixture was taken to be halfthe angle separating the extinction points of the driven states. Theresults given in Table 3 show fast response times over a widetemperature range.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=105.8° C., A to C=72.7° C., and C to M=-9.0° C. The phase transitiontemperatures of the achiral base material (i.e., the above-describedmixture without the chiral dopant) were also measured and were found tobe: I to A=106.2° C., A to C=70.5° C., and C to M=-5.6° C. Thus, thesmectic C. temperature range of the mixture was essentially the same asthat of the achiral base.

Comparative Example 2

A mixture was prepared essentially as described in Example 36 using thesame achiral base mixture and 9.7 weight percent 5-octyl-2-4-((R)-2-fluoro-3-(2-(2butoxyethoxy)ethoxy)propoxy)phenyl!pyrimidine aschiral dopant (instead of Example 5). The phase transition temperaturesof the resulting mixture were found to be: I to A=99.5° C., A to C=31.6°C., and C to M=22.8° C. This data shows a severe loss of the smectic C.mesophase range relative to Example 36, which loss effectively preventsthe use of this comparative mixture in liquid crystal display devices.

Examples 37-52

Other devices were constructed using commercially available polyimides(such as RN-305, RN-741, or RN-763 available from Nissan ChemicalIndustries, Japan) in place of nylon 6/6, or using commerciallyavailable cells (such as a DisplayTech cell, available from DisplayTechin Boulder, Colo., or an EHC cell, available from EHC Ltd., Japan).Since the properties measured to characterize the present invention arelargely independent of cell type, a variety of cells could be utilized.Polarization, viscosity, response time, and tilt angle are effectivelyindependent of the alignment system in a cell, although there are minordifferences in some properties (such as better alignment in nyloncells).

Example 37

A device was prepared and evaluated essentially as described in Example36 using a mixture of 5 weight percent 5-octyl-2-(4-(S)-5-oxymethyl-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)-2(3H)furanone)phenyl!pyrimidine(Example 22) as the chiral dopant, 63.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 31.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results are shown in Table 3 below.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=99.7° C., A to C=54.1° C., and C to K=-16.1° C.

Comparative Example 3

Into a flask fitted with a stirrer, a thermometer, and a refluxcondenser was charged KOH (24.6 g, 373 mmol, dissolved in 25 mL water),1,1-dihydroperfluoromethoxyethoxyethoxyethanol (50 g, 125.6 mmol;prepared by sodium borohydride reduction of the corresponding methylester, essentially as described in Example 3 of U.S. Pat. No. 5,262,082(Janulis et al.)), tetrabutylammonium hydrogen sulfate (3.0 g, 8.8mmol), and 1,6-dibromohexane (150 g). The resulting reaction mixture washeated at 100° C. for three hours, cooled to room temperature, anddiluted with water (75 mL) and perfluoro-N-methyl morpholine (153 g) ina separatory funnel. The resulting lower fluorochemical phase wasremoved from the funnel, and the solvent was distilled at ambientpressure. The resulting residue was distilled, and the fraction boilingat 83°-97° C. at 0.3 torr was collected. GC/MS analysis of this fractionshowed that it contained 12 area % dibromohexane, 71 area % desired6-(1,1-dihydroperfluoro(methoxyethoxyethoxyethoxy))-1-bromohexane (CF₃O(CF₂ CF₂ O)₂ CF₂ CH₂ O(CH₂)₆ Br), and 7 area % CF₃ O(CF₂ CF₂ O)₂ CF₂CH₂ O(CH₂)₆ OCH₂ CF₂ (OCF₂ CF₂)₂ OCF₃.

Using essentially the procedure of Example 8,5-hydroxy-2-(4-(dihydro-5-(R)-oxymethyl-3-(R)-hexyl-2(3H)-furanone)phenyl)pyrimidine(0.20 g, 0.54 mmol) was combined with potassium carbonate (0.09 g, 0.65mmol) and6-(1,1-dihydroperfluoro(methoxyethoxyethoxyethoxy))-1-bromohexane (0.30g, 0.54 mmol) in acetonitrile (20 mL) to yield 0.18 g of product, a90:10 mixture of cis/trans dihydrofuranone isomers (as determined by ¹ Hnuclear magnetic resonance spectroscopy).

A device was prepared and evaluated essentially as described in Example36 using a mixture of 5 weight percent of the product(5-(6-(1,1-dihydroperfluoro(((2-methoxyethoxy)ethoxy)ethoxy)hexyloxy-2-(4-(dihydro-5-(R)-oxymethyl-3-(R)-hexyl-2-(3H)-furanone)phenyl)pyrimidine,prepared as described above), 63.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 31.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results shown in Table 3 indicate that Example 37 exhibits a muchhigher polarization than that of this Comparative Example at similarconcentrations of chiral dopant. Thus, this data shows the importance ofthe position of the chiral moiety relative to the fluorochemical group.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=100.6° C., A to C=51.5° C., and C to K=<-10° C.

Example 38

A device was prepared and evaluated essentially as described in Example36 using a mixture of 5 weight percent 5-octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 3) as the chiral dopant, 63.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 31.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results given in Table 3 show a low viscosity for the mixture, whichprovides a fast response time in spite of the low polarizationexhibited.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=101.1° C., A to C=54.5° C., and C to K=below room temperature.

Example 39

A device was prepared and evaluated essentially as described in Example36 using a mixture of 20 weight percent 5-octyl-2-4-((R)-2-hydroxy-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 3) as the chiral dopant, 53.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine(prepared essentially by the methods described in U.S. Pat. No.5,262,082 (Janulis et al.)), and 26.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results given in Table 3 show a low viscosity for the mixture, whichprovides a fast response time in spite of the low polarizationexhibited.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=96.8° C., A to C=54.3° C., and C to K=below room temperature.

Example 40

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-octyl-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 5). The results given in Table 3 show very fast response times,high polarizations, and low viscosities. In addition, the response timesare relatively temperature-independent.

Example 41

A device was prepared and evaluated essentially as described in Example36 using a mixture of 50.1 weight percent 5-octyl-2-(4-(S)-5-oxymethyl-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)-2(3H)furanone)phenyl!pyrimidine(Example 22) as the chiral dopant, 33.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine(prepared essentially by the methods described in U.S. Pat. No.5,262,082 (Janulis et al.)), and 16.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine(prepared essentially as described in U.S. Pat. No. 5,262,082). Theresults given in Table 3 show very fast response times and highpolarization.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=96.6° C., A to C=51.5° C., and C to K=21.4° C. The phase transitiontemperatures of the achiral base material (i.e., the above-describedmixture without the chiral dopant) were also measured and were found tobe: I to A=99.5° C., A to C=53.8° C., and C to K=<-10° C. Thus, the useof this chiral compound of the invention (Example 22) at highconcentration in an achiral base mixture provides minimal suppression ofthe smectic C. mesophase.

Example 42

A device was prepared and evaluated essentially as described in Example36 using a mixture of 10 weight percent 5-octyloxy-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 10) as the chiral dopant, 63.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 31.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results are shown in Table 3 below.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=106.5° C., A to C=60.5° C., and C to K=<-10° C.

Comparative Example 4

2-(S)-fluorooctanol (3.0 g, 20.2 mmol; which can be prepared by theprocedure described by H. Nohira et al. in Mol. Cryst. Liq. Cryst. 180B,379-88 (1990)) was combined with toluene sulfonyl chloride (4.0 g, 21.2mmol), ethyl diisopropyl amine (5.2 g, 40.4 mmol), anddimethylaminopyridine (123 mg, 1.0 mmol) in methylene chloride (50 mL).The resulting mixture was stirred at room temperature overnight. Theresulting crude tosylate product was purified by flash chromatography onsilica gel, eluting with 10 parts by volume of hexane and 1 part byvolume of ethyl acetate.

A three-necked flask equipped with a magnetic stir bar, a condenser, anda nitrogen inlet was charged with potassium carbonate (380 mg, 2.74mmol) and acetonitrile (20 mL). With stirring,5-hydroxy-2-(4-(1,1-dihydroperfluoro-2-(butoxyethoxy)ethoxy)phenyl)pyrimidine(1.5 g, 2.49 mmol; prepared essentially as in Example 18 above withsubstitution of C₄ F₉ OC₂ F₄ OCF₂ CH₂ OSO₂ CF₃ (4.86 g, 8.6 mmol) for3-(2-2-(nonafluorobutoxy)tetrafluoroethoxy!-2,2-difluoroethoxy)-(R)-2-fluoropropyl-1-p-toluenesulfonate)was slowly added to the resulting mixture. The mixture was stirred atroom temperature for 30 minutes. 1-p-toluenesulfonoxy-2-(S)-fluorooctane(0.75 g, 2.49 mmol) was then added to the stirred mixture. The mixturewas heated to reflux overnight and then poured into a separatory funnelcontaining water (˜20 mL). The resulting layers were separated, and theaqueous phase was extracted with diethyl ether and purified bychromatography (essentially as in Example 8 above), eluting with 10parts by volume of hexane and 1 part by volume of ethyl acetate. Theyield of desired product was 1.4 g. The structure of the product wasconfirmed by ¹ H and ¹⁹ F nuclear magnetic resonance spectroscopy.

A device was prepared and evaluated essentially as described in Example36 using a mixture of 10 weight percent of the product(5-((S)-2-fluorooctyloxy)-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine,prepared essentially as described above), 63.3 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 31.6 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results shown in Table 3 indicate that Example 42 exhibits a muchhigher polarization than that of this Comparative Example (whicheffectively does not respond to an electric field) at similarconcentrations of chiral dopant. Thus, this data shows the importance ofthe position of the chiral moiety relative to the fluorochemical group.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=101° C., A to C=56.5° C., and C to K=0.1° C.

Example 43

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-octyl-2-4-((S)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 4). The results given in Table 3 show very fast response times,high polarizations, and low viscosities. In addition, the response timesare relatively temperature-independent.

Example 44

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-hexyl-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 8). The results given in Table 3 show very fast response times,high polarizations, and low viscosities. In addition, the response timesare relatively temperature-independent.

Example 45

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-octyloxy-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 10). The results given in Table 3 show very fast responsetimes, high polarizations, low viscosities, and a very broad smectic C.temperature range. In addition, the response times are relativelytemperature-independent.

Example 46

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-((R)-2-fluorooctyloxy)-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 18). The results given in Table 3 show very fast responsetimes, high polarizations, and low viscosities.

Example 47

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-((S)-2-fluorooctyloxy)-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 19). The results given in Table 3 show very fast responsetimes, high polarizations, and low viscosities.

Example 48

A device was prepared and evaluated essentially as described in Example36 using a mixture of 10.2 weight percentN-(4-octyloxy)phenyl-(S)-5-((2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)methyl-2-oxazolidinone(Example 20), 59.9 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 29.9 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results given in Table 3 show high polarizations at low chiraldopant concentration.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=93.7° C., A to C=41.9° C., and C to K=<-10° C.

Example 49

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-hexyloxy-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 9). The results given in Table 3 show very fast response times,high polarizations, low viscosities, and a very broad smectic C.temperature range. In addition, the response times are relativelytemperature-independent.

Example 50

A device was prepared and evaluated essentially as described in Example36 using a mixture of 5 weight percent 5-octyl-2-4-((R)-2-fluoro-3-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 5) and 95 weight percent 5-heptyl-2-4-(2-(2-(pentaafluoroethoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)phenyl!pyrimidine(prepared essentially as described in U.S. Pat. No. 5,262,082 (Januliset al.)). The results given in Table 3 show a low viscosity for themixture, which provides a very fast response time in spite of the lowpolarization exhibited.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=84.2° C., A to C=53.0° C., C to K=8.4° C., and K to C=29.1° C.

Example 51

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-octyl-2-4-((R)-2-fluoro-3-(2-(2-(2-(trifluoromethoxy)tetrafluoroethoxy)tetrafluoroethoxy)-2,2,-difluoroethoxy)propoxy)phenyl!pyrimidine(Example 11). The results given in Table 3 show very fast responsetimes, high polarizations, and low viscosities.

Example 52

A device was prepared and evaluated essentially as described in Example36 using 100 weight percent 5-octyl-2-4(nonafluorobutoxy)tetrafluoroethoxy-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-octadecafluorodecyloxy)propoxy)phenyl!pyrimidine(Example 13). The results given in Table 3 show a fast response time, ahigh polarization, and a low viscosity.

Example 53

A device was prepared and evaluated essentially as described in Example36 using a mixture of 10 weight percent (S)-5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)methyl-2-oxazolidinone)phenyl!pyrimidine(Example 33), 60 weight percent 5-octyl-2-4-(6-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy)phenyl!pyrimidine,and 30 weight percent 5-octyl-2-4-(2-(2-(nonafluorobutoxy)tetrafluoroethoxy)-2,2-difluoroethoxy)phenyl!pyrimidine.The results given in Table 3 show high polarizations at low chiraldopant concentration.

In addition, the phase transition temperatures of the mixture weremeasured essentially as described above and were found to be: I toA=105.5° C., A to C=57.3° C., and C to K=16.4° C.

                  TABLE 3                                                         ______________________________________                                        Reduced                                                                       Temper-                                                                       ature       Polari-  Response Smectic                                                                              Tilt                                     (T-T.sub.c, zation   Time     Viscosity                                                                            Angle                                    °C.) (nC/cm.sup.2)                                                                          (μs)  (mPa · s)                                                                   (degrees)                                ______________________________________                                        Example                                                                              -1.40    7.40     16     11.8   26.00                                  36     -2.40    7.90     23     18.2   27.25                                         -5.40    8.90     24     21.3   29.75                                         -10.90   9.60     31     29.7   32.50                                         -15.70   10.40    37     38.5   33.50                                         -25.80   11.20    52     58.2   34.00                                         -35.70   12.20    80     97.6   34.00                                         -45.70   13.40    135    180.9  34.50                                  Example                                                                              -30.1    20.4                   30.6                                   37                                                                            Compar-                                                                              -27.5    5.2                    29.2                                   ative                                                                         Example                                                                        3                                                                            Example                                                                              -1       1.3      42     5.46                                          38     -5       1.9      90     17.1   24                                            -10      1.9      120    22.8   25.5                                          -15      2.2      145    31.9   26.5                                          -25      2.6      200    50.96  28.5                                   Example                                                                              -2       5.8      17     9.86   19                                     39     -5       7.3      32     23.36  22                                            -15      9.8      52     50.96  27.5                                          -25      10.8     90     97.2   29                                            -30      11.7     125    146.25 29.5                                          -40      13       280    364.55 29.5                                   Example                                                                              -3.1     81.1     3.9    31.6   22.4                                   40     -6.5     90.7     4.4    39.9   23.45                                         -14      107.6    5.3    57.0   24.85                                         -19.1    118.7    6.2    73.6                                                 -25.5    127.6    7.1    90.6   25.95                                         -36.9    146.2    9.9    144.7  26.4                                          -48.5    160.9    15     241.3  26.3                                   Example                                                                              -6.5     178      7.5    133.5                                         41     -16.5    213      12.0   255.6                                         Example                                                                              -36.5    11       57     71.5   30.8                                   42                                                                            Compar-                                                                              -32.5    1.3      infinite                                             ative                                                                         Example                                                                        4                                                                            Example                                                                              -0.90    66.00                  20.55                                  43     -3.00    75.00    3.30   26.07  21.65                                         -6.00    84.00    3.70   32.74  22.85                                         -8.60    92.00    4.20   40.70  23.75                                         -11.80   99.00    4.60   47.97  24.5                                          -15.80   110.00   5.10   59.10  25.25                                         -20.90   116.00   5.70   69.65  25.85                                         -23.90   122.00   6.10   78.39  26.1                                   Example                                                                              -6.30    79.90    3.40   28.74  22.9                                   44     -10.90   94.20    4.20   41.86  24.5                                          -16.00   109.40   5.40   62.51  26.05                                  Example                                                                              -2.00    102.80   4.00   43.98  31.35                                  45     -9.00    117.90   4.40   55.49  33.3                                          -22.00   140.40   5.70   85.60  34.85                                         -41.40   166.60   8.60   153.25 35.4                                          -74.20   200.20   32.00  685.26 34.65                                  Example                                                                              -0.90    70.90    6.00   45.54  30.45                                  46     -6.70    92.20    7.00   69.10  33.45                                         -21.30   84.80    14.00  127.10 35.4                                   Example                                                                              -1.00    133.40   7.50   105.74 34.05                                  47     -5.40    155.80   8.10   133.37 34.65                                         -9.60    178.50   8.50   160.35 34.7                                   Example                                                                              -4.00    42.30    8.90   37.65  49.10                                  48     -12.30   52.60    13.30  69.96  54.50                                         -20.40   60.10    19.40  116.59 57.20                                         -28.50   65.70    30.80  202.36 58.70                                         -36.90   68.90    54.80  377.57 59.50                                         -45.10   72.00    110.00 792.00 59.90                                  Example                                                                              -7.40    96.00    3.70   35.52  28.35                                  49     -20.80   122.30   4.70   57.48  31.35                                         -37.50   149.90   6.10   91.44  32.55                                         -67.10   195.20   13.70  267.42 32.60                                  Example                                                                              -2.20    7.40                   13.25                                  50     -3.90    8.50                   16.7                                          -6.90    12.30    6.80   8.36   18.55                                         -10.00   13.90    9.30   12.93                                                -11.90   14.40    10.70  15.41  20.4                                          -13.90   15.70    11.60  18.21  20.85                                         -20.20   18.00    14.70  26.46  20.05                                         -25.00   19.30    18.20  35.13  22.8                                   Example                                                                              -5.00    88.00    4.20   36.96  22.75                                  51     -20.90   110.70   6.20   68.63  24.4                                   Example                                                                              -3.00    77.20    6.40   49.41  0                                      52                                                                            Example                                                                              0        30.7     3      9.21   17                                     53     -5       44.2     6      26.52  23.5                                          -15      55.8     9.5    53.01  28                                            -20      59.5     11.5   68.425 28.5                                          -30      65.9     19     125.21 29                                            -40      68.5     36     246.6  29                                     ______________________________________                                    

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention.

We claim:
 1. Fluorine-containing, chiral liquid crystal compounds thathave smectic mesophases or latent smectic mesophases and that arerepresented by the general formula (I): ##STR53## where M, N, and P areeach independently selected from the group consisting of ##STR54## a, b,and c are each independently zero or an integer of from 1 to 3, with theproviso that the sum of a+b+c be at least 1;each A and B arenon-directionally and independently selected from the group consistingof a covalent bond,

    --C(═O)--O--, --C(═O)--S--, --C(═O)--Se--,

    --C(═O)--Te--, --(CH.sub.2 CH.sub.2).sub.k

where K is 1 to 4,

    --CH═CH--, --C.tbd.C--, --CH═N--, --CH.sub.2 --O--, --C(═O)--, and --O--;

each X, Y, and Z are independently selected from the group consisting of--H, --Cl, --F, --Br, --I, --OH, --OCH₃, --CH₃, --CF₃, --OCF₃, --CN, and--NO₂ ; each l, m, and n are independently zero or an integer of 1 to 4;D is non-directionally selected from the group consisting of a covalentbond, ##STR55## and combinations thereof, where r and r' areindependently integers of 0 to about 20, s is independently an integerof 1 to about 10 for each (C_(s) H_(2s) O), t is an integer of 1 toabout 6, and p is an integer of 0 to about 4; R is selected from thegroup consisting of

    --O--((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q+1-v --(R').sub.v,

    --((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q+1-v --(R').sub.v,

    --C(═O)--O--C.sub.q H.sub.2q+1-v --(R').sub.v,

    --O--(O═)C--C.sub.q H.sub.2q+1-v --(R').sub.v, ##STR56## where each R' is independently selected from the group consisting of --Cl, --F, --CF.sub.3, --NO.sub.2, --CN, --H, --C.sub.q H.sub.2q+1, --O--(O═)C--C.sub.q H.sub.2q+1, --C(═O)--O--C.sub.q H.sub.2q+1, --Br, --OH, and --OC.sub.q H.sub.2q+1 ;

q' is independently an integer of 1 to about 20 for each (C_(q) H_(2q')--O); q is an integer of 1 to about 20; w is an integer of 0 to about10; v is an integer of 0 to about 6; each v' is independently an integerof 0 to about 6; g is an integer of 1 to about 3; each D isindependently and non-directionally selected from the group set forthfor D above, with the proviso that the ring containing D has from about3 to about 10 ring atoms; each W is independently selected from thegroup consisting of N, CR', and SiR'; and R is chiral or achiral; andR_(f) ' is --R*--D--(O)_(x) --CH₂ --D'--R_(f), where R* is a cyclic oracyclic chiral moiety selected from the group consisting of

    --O--((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q-v --(R').sub.v --,

    --((C.sub.q' H.sub.2q'-v' --(R').sub.v')--O).sub.w --C.sub.q H.sub.2q-v --(R').sub.v --,

    --C(═O)--O--C.sub.q H.sub.2q-v --(R').sub.v --,

    --O--(O═)C--C.sub.q H.sub.2q-v --(R').sub.v --, ##STR57## where each R' is --F; q' is independently an integer of 1 to about 20 for each (C.sub.q' H.sub.2q' --O); q is an integer of 1 to about 20; w is an integer of 0 to about 10; v is an integer of 1 to about 3; each v' is independently an integer of 0 to about 6; g is an integer of 1 to about 3; each D is independently and non-directionally selected from the group set forth for D above, with the proviso that the ring containing D has from about 3 to about 10 ring atoms; each W is independently selected from the group consisting of N and CH; and with the proviso that R* is chiral; D and D' are each independently and non-directionally selected from the group set forth for D above; x is an integer of 0 or 1; and R.sub.f is fluoroalkyl, perfluoroalkyl, fluoroether, or perfluoroether.


2. Fluorine-containing, chiral liquid crystal compounds that havesmectic mesophase or latent smectic mesophase and that are representedby the general formula (II):

    R" --(O).sub.j --G--(OCH.sub.2).sub.j --R*--(C.sub.s H.sub.2s O).sub.t C.sub.r' H.sub.2r' --R.sub.f                              (II)

where R" is (R')_(v) --C_(q) H_(2q+1-v), where q is an integer of 2 toabout 10, each R' is independently selected from the group consisting ofhydrogen, fluorine, chlorine, methyl, and perfluoromethyl, and v is aninteger of 1 to about 3; j is an integer of 0 or 1; G is selected fromthe group consisting of ##STR58## R* is selected from the groupconsisting of --C_(q) H_(2q-v) --(R')_(v) -- and ##STR59## where R' is--F, q is an integer of 1 to about 4, v is an integer of 1 to about 3, Wis N or CH, and D is a cyclic or acyclic chiral moiety --C(═O)--O-- or--CH₂ --; s is an integer of 1 to about 6; t is an integer of 0 or 1; r'is an integer of 1 to about 3; and R_(f) is selected from the groupconsisting of --C_(q) F_(2q) X', --R_(f) "--R_(h), and --(C_(x) F_(2x)O)_(z) C_(y) F_(2y+1), where q is an integer of 1 to about 6, X' isfluorine, R_(f) " is a linear or branched, perfluorinated alkylene grouphaving from about 2 to about 4 carbon atoms and optionally containingone or more catenary ether oxygen atoms, R_(h) is a linear or branchedalkyl group having from about 2 to about 7 carbon atoms and optionallycontaining one or more catenary ether oxygen atoms, x is independentlyan integer of i to about 10 for each (C_(x) F_(2x) O), y is an integerof 1 to about 8, and z is an integer of 1 to about 5.